Nonlinear optical crystal optimized for Ytterbium laser host wavelengths

ABSTRACT

A material for harmonic generation has been made by substitutional changes to the crystal LaCa 4  (BO 3 ) 3  also known as LaCOB in the form Re1 x Re2 y Re3 z Ca 4 (B0 3 ) 3 O where Re1 and Re2, (rare earth ion 1 and rare earth ion 2) are selected from the group consisting of Sc, Yttrium, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; Re3 is Lanthanum; and x+y+z=1.

[0001] The United States Government has rights in this inventionpursuant to Contract No. W-7405-ENG-48 between the United StatesDepartment of Energy and the University of California for the operationof Lawrence Livermore National Laboratory.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to solid-state laser materials, andspecifically to noncritical phase matching laser materials capable ofnon-linear harmonic conversion of a specific wavelength.

[0004] 2. State of Technology

[0005] Ytterbium doped laser hosts emit in the wavelength range between970 nm and 1047 nm. Some examples of these crystals are Ytterbium dopedstrontium fluoro-apatite (i.e., Yb:SFAP), Ytterbium doped yttriumaluminum garnet (Yb:YAG), Ytterbium aluminum garnet (YbAG), Yb dopedglass (Yb:glass), Yb doped potassium gadolinium tungstate(Yb:KGd(WO4)2), and Ytterbium doped fused silica (Yb:SiO₂). Each hosthas specific application and utility. Collectively, these lasers emit inthe range of 970-1045 nm. For example, Yb:SFAP emits at several specificwavelengths, such as 1047 and 985 nm. As another example, Yb:YAG has atunable laser emission between 1020 and 1045 nm, with a peak emissionoccurring at 1030 nm.

[0006] Frequency conversion of such lasers discussed above has beenfound to be useful for many applications. For example, frequencydoubling of the 1029-nm emission of Yb:YAG leads to laser light at thewavelength of 514.5 nm. This specific wavelength is emitted by theArgon-ion laser and is a wavelength that has many beneficial and usefulapplications. For example, the 514.5-nm wavelength is useful in thebiotechnology field for cell sorting of biological compounds. Byutilizing frequency conversion, a solid-state frequency converted laserhas the potential to replace the Ar-ion gas laser for this specificwavelength.

[0007] Background information on improved frequency mixing crystals forharmonic generation of laser beams is contained in U.S. Pat. No.5,123,022 entitled “Frequency Mixing Crystal,” to Ebbers et al.,patented Jun. 16, 1992 including the following: “The improvement of saidmeans of harmonic generation comprising a crystal having the chemicalformula X₂Y(NO₃)5.2nZ₂O wherein X is selected from the group consistingof Li, Na, K, Rb, Cs, and Tl; Y is selected from the group consisting ofSc, Y, La, Ce, Nd, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, andIn; Z is selected from the group consisting of H and D; and n rangesfrom 0 to 4.”

[0008] Background information on frequency mixing crystals bycongruently melted compositions including a lanthanide is contained ininternational application No. WO 96/26464 entitled “Non-linear CrystalsAnd Uses Thereof,” to Gerard et al., patented Feb. 16, 1996, includingthe following: “The crystals are prepared by crystallizing a congruentmelting composition of general formula: M₂LnO(BO₃)₃, wherein M is Ca orCa partially substituted by Sr or Ba, and Ln is a lanthanide from thegroup which includes Y, Gd, La and Lu. Said crystals are useful asfrequency doublers and mixers, as an optical parametric oscillator or,when partially substituted by Nd³⁺, as a frequency doubling crystal.

[0009] Accordingly, a need exists to improve solid-state frequencymaterials for specific wavelengths. An ideal crystal is not difficult togrow, has a high nonlinear optical coefficient, has a high opticaldamage threshold, and birefringence and contains dispersion propertiesthat allow for noncritical phasematching at specific wavelengths. Thepresent invention involves such a crystal.

SUMMARY OF THE INVENTION

[0010] Accordingly, the present invention provides a frequencyconversion crystal which is noncritically phasematched having a generalchemical formula

[0011] Re1xRe2yRe3zCa₄(B0₃)₃O, wherein Re1 and Re2 are selected from thegroup consisting of Sc, Yttrium, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho,Er, Tm, Yb, and Lu; Re3 is Lanthanum; and x+y+z=1.

[0012] Another aspect of the present invention provides a laser systemhaving incorporated therein the frequency mixing crystal describedherein.

[0013] Accordingly, the present invention provides an external orintracavity frequency conversion crystal with an increased birefringenceto make such a crystal suitable for noncritical phasematching orsubstantially noncritical phasematching of wavelengths between about 970and about 1047 nm, wavelengths emitted by Ytterbium doped laser hosts.Such a crystal is useful for medical and biological applications whereina specific wavelength can be applied in a single shot or variablerepetition rate pulsed format.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The accompanying drawings, which are incorporated into and form apart of the disclosure, illustrate an embodiment of the invention and,together with the description, serve to explain the principles of theinvention.

[0015]FIG. 1(a) illustrates the external morphology of a crystalproduced by the present invention.

[0016]FIG. 1(b) illustrates the relative orientation of crystallographic(X, Y, Z) axes with regard to crystallographic axes (a, b, c) of amonoclinic structure.

[0017]FIG. 2 shows a plot of birefringence versus rare earth ion size toillustrate the sensitivity of the birefringence of a crystal, such as inthe present invention, to the size of a trivalent cation.

[0018]FIG. 3 is a basic schematic of an apparatus incorporating thecrystal of the present invention in an intra-cavity configuration.

[0019]FIG. 4 is a basic schematic of an apparatus incorporating thecrystal of the present invention in an external cavity configuration.

DETAILED DESCRIPTION OF THE INVENTION

[0020] Referring now to the following detailed information, and toincorporated materials; a detailed description of the invention,including specific embodiments, is presented. The detailed descriptionserves to explain the principles of the invention.

[0021] Unless otherwise indicated, numbers expressing quantities ofingredients, constituents, reaction conditions and so forth used in thespecification and claims are to be understood as being modified by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the specification and attached claimsare approximations that may vary depending upon the desired propertiessought to be obtained by the subject matter presented herein. At thevery least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques. Notwithstanding that the numerical ranges and parameterssetting forth the broad scope of the subject matter presented herein areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contain certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

[0022] General Description

[0023] The present invention improves the performance of Ytterbium dopedlaser crystals that are intracavity, (i.e., the frequency conversioncrystal is placed within a laser cavity), or externally frequencydoubled, (i.e., the frequency conversion crystal is positioned externalto a laser cavity). Specifically, the frequency conversion process isimproved through the utilization of a frequency conversion crystal thatis noncritically phasematched for the wavelength of interest.Noncritical phasematching occurs when the crystal is phasematched forpropagation down one of the dielectric axis of a nonlinear opticalcrystal and allows for better conversion efficiency of lasers,particularly multimode lasers.

[0024] Accordingly, the present invention modifies properties offrequency conversion crystals such that these crystals can be made tononcritically phasematch or substantially noncritically phasematchwavelengths between about 970 nm and about 1042 nm, the wavelength rangeover which Ytterbium doped laser hosts have an emission output.

[0025] Specific Description

[0026] The present invention alters the birefringence and dispersion oflanthanum calcium oxyborate (LaCOB) to make a new crystal, which iscapable of noncritical phasematching (NCPM). Phase matching in generaloccurs for certain crystallographic directions. If a light ray deviatesfrom this phase-matched direction, the condition for phase matching nolonger occurs. This places limitations on the allowable angulardivergence of an input coherent source. In addition, because doublerefraction, i.e., birefringence, occurs in anisotropic materials such asin the present invention, the radiated wave and the polarization wavepropagate in different optical angular directions within the crystal,also known as “walk-off,” thereby reducing the interaction distancewithin the frequency converting crystal. Phase matching under theseconditions is called critical phase matching (CPM). For certaincrystallographic directions, a larger angular deviation is tolerated,resulting in a greater divergence from the phase-matched direction andno first-order walk-off occurs. This condition is termed non-criticalphase matching (NCPM).

[0027] Accordingly, the optical birefringence and dispersion propertiesof a crystal, such as, but not limited to, LaCOB, can be predeterminedby varying growth parameters so that phase matching occurs forcrystallographic directions along which substantially NCPM is possible.In particular, the present invention varies specific growth parametersby the addition of other rare earth ions (and/or ions including yttriumand scandium) to the crystal growth melt during crystal growth in acontrolled fashion to produce a crystal that is non-critically phasematched at a specific wavelength.

[0028] Attempts by others to grow crystals with good optical qualitysuch as that of the present invention have been unsuccessful.Specifically, the present invention modifies the crystal LaCa₄(B0₃)₃O,also known as LaCOB by a substitutional change of the formRe1xRe2yRe3zCa₄(B0₃)₃O, where Re1 and Re2 (i.e., rare earth ion 1 andrare earth ion 2), can be selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu,Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Re3 is lanthanum (La), and acondition for variables x, y, and z is x+y+z=1.

[0029] Crystal Growth

[0030] The crystal of the present invention is prepared by melting thefollowing oxides into a 3 inch high×3 inch diameter iridium crucible:(Re1₂O₃)x, (Re2₂O₃)y, (Re3₂O₃)z, CaO₄, B₂0₃, coupled with the conditionx+y+z=1, in stoichiometric proportions. Between about 800 and about 1200grams of the oxide and carbonate starting materials is used to grow thecrystal. Boules of LaCOB are subsequently grown from a melt using thestandard Czochralski pulling method. A seed of about 5 mm diameter isintroduced at the top of the molten material and a crystal is grown byslowly pulling and rotating the crystal, while carefully controlling thetemperature of the melt to maintain crystal diameter. A similar methodfor growing crystals of the present invention is disclosed inInternational Application No. WO 96/26464 entitled “Non-linear CrystalsAnd Uses Thereof,” by Gerard et al., which is fully incorporated hereinby reference in its entirety. Although cracking is problematic, largecrack free crystals are obtained by careful alignment of the seedcrystal along a preferred growth direction (i.e., one of the dielectricaxis) and by careful control of the cooling cycle. The material meltscongruently with a growth rate of about 0.5 to about 1.5 mm/h. Exemplarygrowth sizes are from about 2.5 to about 3.0 centimeter in diameter withlengths from about 5.0 to about 15 centimeters. However, largerdimension crucibles capable of growing a crystal such as that of thepresent invention, with sufficient diameters and lengths, may be used togrow larger sized crystals if desired. The resultant crystal is clear,with good optical quality (i.e., a small number of optical defectsnumbering from about ≦10² to about 10³/cm³) and the mechanicalproperties of the present crystal allow polishing by conventionalmethods known in the art.

[0031] Crystal Properties

[0032] The crystal described herein, e.g., a modification of LaCOB,belongs to the calcium rare-earth oxyborate family that crystalizes inthe monoclinic biaxial crystal system and as one embodiment, may be usedwith Ytterbium lasers.

[0033] Referring to FIG. 1(a), the values of the unit cell constants(i.e., crystallographic axis) are a=8.095(7) angstroms 22, b=16.018(6)angstroms 24, c=3.558(8) angstroms 26, and β=101.43 degrees (not shown).The crystal belongs to the Cm space group and the number of the formulaunit is Z=2. Monoclinic biaxial crystals such as that of the presentinvention display three different refractive indices, (i.e.,n_(X)<n_(Y)<n_(Z)), along the crystallographic axis (X, Y, Z) 28 that donot correspond to crystallographic reference axis a 22, b, 24, and c 26shown in FIG. 1(a).

[0034]FIG. 1(b) illustrates the relative orientation of (X, Y, Z) 28with regard to the crystallographic axis a 22, b, 24, and c 26, as shownin FIG. 1(a). This orientation as determined by X-ray analysis gives bparallel to Y and normal to the plane in FIG. 1(b), a with respect tothe Z axis equal to 26 degrees, c with respect to the X axis equal to 15degrees, and β is the angle of the present invention's monoclinic unitcell. The crystal of the present invention is substantially transparentfrom about 320 to about 2600 nm and it is resistant to color centerformation (i.e., a point lattice defect which produces opticalabsorption bands in an otherwise transparent crystal). In addition, thecrystal is not sensitive to water, a property that allows for variousoptical anti-reflective coatings to be applied, such as but not limitedto Sol-Gel, e-beam deposited and CVD coatings.

[0035] Crystal Structure Modification

[0036] The condition for type I doubling in the crystal of the presentinvention or its isomorphs in the alpha-gamma principle plane is shownin equation 1,

ΔK=0=[2n _(y)(λ₁)ω₁ /c]−[n _(xz)(λ₂)ω₂ /c],

[0037] where φ is the angle from the x dielectric axis in the x-z plane,n_(x), ny, nz, are the principle refractive wavelength dependent indicesand nxz is given by:

n _(xz) =n _(x) n _(y) /[n ² _(x)+(n ² _(z) −n ² _(x)) sin²(φ)]^(0.5).  (1a)

[0038] The angular sensitivity, β_(φ), is the change in ΔK with angle φ,shown in equation 2.

β_(φ) =dΔK/d _(φ)=[(n _(z) −n _(x))(n _(z) +n _(x)) sin (2φ) (n _(x) n_(z))/[n ² _(x)+(n ² _(z) −n ² _(x)) sin² (φ)]^(3/2)]

[0039] As seen from equation (2), the angular sensitivity β_(φ), forType I doubling in the crystal of the present invention and itsisomorphs, is proportional to the X-Z principle plane birefringence(n_(z)−n_(x)). In turn, the figure of merit used for comparison againstother materials is the threshold In turn, the figure of merit used forcomparison against other materials is the threshold power P_(th),proportional to (β_(φ/d) _(eff))², where β_(φ) is the angularsensitivity, the rate of wavevector mismatch with respect to angularorientation, and d_(eff) is the effective nonlinearity at that specificcrystal orientation. The lower the threshold power, which is dependenton the α-γ principle birefringence plane, the better the material is forfrequency conversion. For noncritical phasematching, the threshold poweris zero. The present invention thus modifies the α-γ principle planebirefringence of crystal 20, shown in FIG. 1, and thus modifies thethreshold power of the material by substitutional changes to crystal 20by the addition of rare earth ions (and/or ions including yttrium andscandium) to the crystal growth melt during crystal growth.

[0040] Turning to FIG. 2, a measured X-Z principle plane birefringenceof GdCOB and YCOB and an extrapolated value for LaCOB is displayedrelative to the ionic radius of the respective cation. FIG. 2illustrates the sensitivity of the birefringence of a crystal, such asin the present invention, to the size of a trivalent cation (i.e., Y vs.Gd vs. La). Thus, crystal 20 shown in FIG. 1, is capable of beingengineered to noncritically phasematch at an appropriate wavelength byincorporating a trivalent cation, such as La, into the into the growthcomposition during the growth process.

[0041] The present invention will be more fully understood by referenceto the following two examples, which are intended to be illustrative ofthe present invention, but not limiting thereof.

EXAMPLE I

[0042] Gd_(x)La_(1-x)Ca₄(B0₃)₃O, with x in the range between about 0 andabout 0.5, y=1-x, and z=0, is crystalized from a solution of Gd₂O₃, CaO,B₂O₃, and La₂O₃. The resulting crystal is useful as a high-efficiencyfrequency conversion crystal for wavelengths between about 1030 nm andabout 1047 nm. Such a crystal allows noncritical phasematching by lasermaterials such as Yb:SFAP, Yb:TAG, Yb:SiO2, and Yb:Glass.

EXAMPLE II

[0043] Gd_(x)La_(1-x)Ca₄(B0₃)₃O, with x in the range between about 0.7and about 1.0, y=1−x, and z=0, is crystalized from a solution of Gd₂O₃,CaO, B₂O₃, and La₂O₃.

[0044] The resulting crystal is useful as a high-efficiency frequencyconversion crystal for wavelengths between about 970 nm and about 985nm. Such a crystal allows noncritical phasematching by laser materialssuch as Yb:SFAP, Yb:YAG, Yb:SiO2, and Yb:Glass, when the peak laseremission is suppressed.

[0045] A laser apparatus generally designated by the reference numeral30, into which the new material of the present invention may beincorporated, is illustrated schematically in FIG. 3. Laser apparatus30, includes a laser gain medium 6, such as but not limited to Yb: laserhost materials, for example Yb:SFAP, Yb:YAG, Yb:SiO2, and Yb:Glass, anexcitation source 3, such as another laser, a laser diode or a laserdiode array(s) to stimulate laser excitation of gain medium 6 eitherlongitudinally or transversely. However, transverse pumping of the lasergain medium by other sources, such as LEDs or flashlamps may also beemployed in conformance with the specifications of the presentinvention. A rear high reflector 8 (e.g., having a reflectivity greaterthan 98% for a predetermined wavelength), and an output coupler 10,(i.e., it allows extraction of the energy from a laser system) arearranged to form a resonant laser cavity (i.e., the laser apparatus)that includes gain medium 6. Such a resonant cavity of the presentinvention is capable of generating a beam 12 of coherent electromagneticradiation having an emission wavelength between about 970 nm and about1047 nm. A crystal 14 of the present invention can be adapted, (i.e.,cut at the proper angles), and placed as an intracavity (i.e., withinthe resonant laser cavity) frequency conversion device to laserapparatus 30 to frequency double an emission wavelength. Such afrequency doubling method is capable of producing a wavelength betweenabout 485 nm and about 523 nm, preferably 514 nm, by virtue of thenon-linear frequency-conversion properties of crystal 14.

[0046] As an alternative embodiment, FIG. 4 shows laser apparatus 30into which crystal 14 of the present invention may be incorporated as anextracavity device (i.e., external to the resonant laser cavity). Laserapparatus 30, includes a laser gain medium 6, such as but not limited toYb: laser host materials, for example Yb:SFAP, Yb:YAG, Yb:SiO2, andYb:Glass, and a similar excitation source 3 discussed herein before tostimulate laser excitation of gain medium 6. A rear high reflector 8 andan output coupler 10, for a predetermined wavelength may be configuredto generate a beam 12 of coherent electromagnetic radiation having anemission wavelength between about 970 nm and about 1047 nm. The presentinvention in this embodiment is thus also capable of producing awavelength between about 485 nm and about 523 nm, preferably 514 nm, byvirtue of the non-linear frequency-conversion properties of crystal 14.

[0047] While the invention may be susceptible to various modificationsand alternative forms, specific embodiments have been shown by way ofexample in the drawings and have been described in detail herein.However, it should be understood that the invention is not intended tobe limited to the particular forms disclosed. Rather, the invention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the followingappended claims.

The invention claimed is:
 1. A material for harmonic generation,comprising: a crystal having a general chemical formulaRe1_(x)Re2_(y)Re3_(z)Ca₄(B0₃)₃O, wherein Re1 and Re2 are selected fromthe group consisting of Sc, Yttrium, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, and Lu; Re3 is Lanthanum; and x+y+z=1.
 2. The materialof claim 1, wherein Re1 is Gd, Re2 is La, and x ranges from about 0 toabout 0.5, y=1−x, and z=0.
 3. The material of claim 2, wherein x rangesfrom about 0 to about 0.7.
 4. The material of claim 1, wherein thecrystal is substantially noncritically phasematched for a predeterminedwavelength.
 5. A laser apparatus, comprising: a laser gain medium, anexcitation means coupled with the gain medium for pumping the gainmedium, a cavity forming means surrounding the gain medium to form aresonant laser cavity, a harmonic generator capable of doubling thefrequency of said radiation, said harmonic generator being a crystalhaving the general chemical formula Re1_(x)Re2_(y)Re3_(z)Ca₄(B0₃)₃O,wherein Re1 and Re2 are selected from the group consisting of Sc,Yttrium, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; Re3is Lanthanum, and x+y+z=1; and an energy extraction means in the cavityforming means to remove laser energy from the cavity.
 6. The apparatusof claim 5, wherein Re1 is Gd, Re2 is La, x ranges from about 0 to about0.5, y=1−x, and z=0.
 7. The apparatus of claim 6, wherein x ranges fromabout 0 to about 0.7.
 8. The apparatus of claim 7, wherein the lasergain medium further comprises a Ytterbium doped laser gain medium havingan emission wavelength between about 970 nm and about 1047 nm.
 9. Theapparatus of claim 8, wherein the crystal is an intracavity device andadapted within a laser cavity to multiply the frequency of saidradiation.
 10. The apparatus of claim 9, wherein the emission wavelengthis doubled.
 11. The apparatus of claim 8, wherein said Ytterbium dopedlaser gain medium is a material selected from Yb:SFAP, Yb:YAG, YbAG,Yb:glass, and Yb:SiO₂.
 12. The apparatus of claim 5, wherein the crystalis external to a laser cavity and adapted to multiply the frequency ofthe radiation.
 13. The apparatus of claim 5, wherein the crystal issubstantially noncritically phasematched.